Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH)

Andrew J. Smith; Allan Young; Simon Rohrbach; Erin F. O'Connor; Mark Allison; Hong-Shuang Wang; Darren L. Poole; Tell Tuttle; John A. Murphy

doi:10.1002/anie.201707914

Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH)

Andrew J. Smith, Allan Young, Simon Rohrbach, Erin F. O'Connor, Mark Allison, Hong-Shuang Wang, Darren L. Poole, Tell Tuttle, John A. Murphy

Research output: Contribution to journal › Article › peer-review

37 Citations (Scopus)

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Abstract

Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on (a) single electron transfer (SET), and (b) hydride delivery reactions to arenes.

Original language	English
Pages (from-to)	13747–13751
Number of pages	5
Journal	Angewandte Chemie International Edition
Volume	56
Issue number	44
Early online date	11 Sept 2017
DOIs	https://doi.org/10.1002/anie.201707914
Publication status	Published - 23 Oct 2017

Keywords

electron-transfer reactions
hydride-transfer pathways
single-electron transfer
hydride delivery reactions

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10.1002/anie.201707914Licence: CC BY 4.0

Smith-etal-ACIE-2017-Electron-transfer-and-hydride-transfer-pathways-in-the-Stoltz-Grubbs-Reducing-SystemFinal published version, 824 KBLicence: CC BY 4.0

John Murphy
- john.murphystrath.acuk
- Pure And Applied Chemistry - Professor
Person: Academic

Electron Transfer and Hydride Transfer Pathways in the Stoltz-Grubbs Reducing System (KOtBu-Et3SiH) - Compounds 54 - 59
Rohrbach, S. (Creator), University of Strathclyde, 12 Sept 2017
DOI: 10.15129/554c14c0-b996-4345-b9a0-e8ea1ef78dc0
Dataset
Data for: "Electron Transfer and Hydride Transfer Pathways in the Stoltz-Grubbs Reducing System (KOtBu-Et3SiH)"
Young, A. (Creator), University of Strathclyde, 12 Sept 2017
DOI: 10.15129/fece83f2-ac55-4020-a865-a57aee7d1368
Dataset
Electron Transfer and Hydride Transfer Pathways in the Stoltz-Grubbs Reducing System Data for Compounds 15-50
Smith, A. (Creator), University of Strathclyde, 12 Sept 2017
DOI: 10.15129/fa911a99-4c39-440c-8834-096263b63695
Dataset

Cite this

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title = "Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH)",

abstract = "Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on (a) single electron transfer (SET), and (b) hydride delivery reactions to arenes.",

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author = "Smith, {Andrew J.} and Allan Young and Simon Rohrbach and O'Connor, {Erin F.} and Mark Allison and Hong-Shuang Wang and Poole, {Darren L.} and Tell Tuttle and Murphy, {John A.}",

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doi = "10.1002/anie.201707914",

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T1 - Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH)

AU - Smith, Andrew J.

AU - Young, Allan

AU - Rohrbach, Simon

AU - O'Connor, Erin F.

AU - Allison, Mark

AU - Wang, Hong-Shuang

AU - Poole, Darren L.

AU - Tuttle, Tell

AU - Murphy, John A.

PY - 2017/10/23

Y1 - 2017/10/23

N2 - Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on (a) single electron transfer (SET), and (b) hydride delivery reactions to arenes.

AB - Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on (a) single electron transfer (SET), and (b) hydride delivery reactions to arenes.

KW - electron-transfer reactions

KW - hydride-transfer pathways

KW - single-electron transfer

KW - hydride delivery reactions

U2 - 10.1002/anie.201707914

DO - 10.1002/anie.201707914

M3 - Article

SN - 1433-7851

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JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 44

ER -

Electron transfer and hydride transfer pathways in the Stoltz-Grubbs reducing system (KOtBu-Et3SiH)

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Electron Transfer and Hydride Transfer Pathways in the Stoltz-Grubbs Reducing System (KOtBu-Et3SiH) - Compounds 54 - 59

Data for: "Electron Transfer and Hydride Transfer Pathways in the Stoltz-Grubbs Reducing System (KOtBu-Et3SiH)"

Electron Transfer and Hydride Transfer Pathways in the Stoltz-Grubbs Reducing System Data for Compounds 15-50

Cite this